The first example of the reactions of cyclopropenes with N-acyliminium cations generated from hydroxylactams

Article abstract of DOI:10.1016/j.tet.2016.06.052

The first example of the reactions of cyclopropenes with N-acyliminium cations is described. 3-(1H-Inden-3-yl)isoindolin-1-ones and cyclopropa[c]isoindolo[2,1-a]quinolones were prepared by BF₃·OEt₂mediated reactions of cyclopropenes

Full text of DOI:10.1016/j.tet.2016.06.052

Accepted Manuscript
The first example of the reactions of cyclopropenes with N-acyliminium cations
generated from hydroxylactams
Anna G. Larina, Vlada E. Nosova, Alexander S. Filatov, Alexander P. Molchanov,
Galina L. Starova, Andrey A. Zolotarev, Vitaly M. Boitsov, Alexander V. Stepakov
PII:
S0040-4020(16)30574-9
10.1016/j.tet.2016.06.052
TET 27866
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 7 April 2016
Revised Date: 6 June 2016
Accepted Date: 20 June 2016
Please cite this article as: Larina AG, Nosova VE, Filatov AS, Molchanov AP, Starova GL, Zolotarev
AA, Boitsov VM, Stepakov AV, The first example of the reactions of cyclopropenes with N-acyliminium
cations generated from hydroxylactams, Tetrahedron (2016), doi: 10.1016/j.tet.2016.06.052.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
Graphical Abstract
Leave this area blank for abstract info.
The first example of the reactions of cyclopropenes with
N-acyliminium cations generated from hydroxylactams
a
a
a
a
a
Anna G. Larina, Vlada E. Nosova, Alexander S. Filatov, Alexander P. Molchanov, Galina L. Starova,
a
b,c
a,d,*
Andrey A. Zolotarev, Vitaly M. Boitsov, and Alexander V. Stepakov
a
Saint-Petersburg State University, University emb. 7/9, St. Petersburg, 199034, Russian Federtion.
b
c
d
Saint-Petersburg Academic University – Nanotechnology Research and Education Centre RAS, Khlopin str. 8/3, St-Petersburg, 194021, Russian Federation.
Pavlov First Saint Petersburg State Medical University, L'va Tolstogo str. 6/8, St. Petersburg 197022, Russian Federation.
Voeikov Main Geophysical Observatory, ul. Karbysheva 7, St. Petersburg 194021, Russian Federation.
R3
R3
R2
R2
R
R1
R3
OH
N
O
N
R1
R2
R' or
R
N
BF ·Et O
3
2
O
O
29-64%
53-74%

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
The first example of the reactions of cyclopropenes with N-acyliminium cations gen-
erated from hydroxylactams
a
a
a
a
Anna G. Larina, Vlada E. Nosova, Alexander S. Filatov, Alexander P. Molchanov, Galina L.
a
a
b,c
a,d,∗
Starova, Andrey A. Zolotarev, Vitaly M. Boitsov, and Alexander V. Stepakov
Saint-Petersburg State University, University emb. 7/9, St. Petersburg, 199034, Russian Federation.
Saint-Petersburg Academic University – Nanotechnology Research and Education Centre RAS, Khlopin str. 8/3, St-Petersburg, 194021, Russian Federation.
Pavlov First Saint Petersburg State Medical University, L'va Tolstogo str. 6/8, St. Petersburg 197022, Russian Federation.
Voeikov Main Geophysical Observatory, ul. Karbysheva 7, St. Petersburg 194021, Russian Federation.
a
b
c
d
ARTICLE INFO
ABSTRACT
Article history:
Received
The first example of the reactions of cyclopropenes with N-acyliminium cations is described. 3-
(1H-Inden-3-yl)isoindolin-1-ones and cyclopropa[c]isoindolo[2,1-a]quinolones were prepared
Received in revised form
Accepted
by BF
3 2
·OEt mediated reactions of cyclopropenes with the N-acyliminium cations, generated
from 2-aryl(benzyl)-3-hydroxyisoindolin-1-ones.
Available online
Keywords:
cyclopropenes
hydroxylactams
N-acyliminium cation
fused-ring systems
indenes
Lewis acids
1
. Introduction
enecarboxylate react with the N-acyliminium cations generated
from 3-hydroxy-2-arylisoindolin-1-ones in the presence of
BF ·OEt to give the corresponding cyclopropa[c]isoindolo[2,1-
a]quinolones in moderate yields. The reaction of N-acyliminium
cations with 1,2,3-triphenylcycloprop-1-ene proceeded smoothly
at room temperature to afford 3-(1H-inden-3-yl)isoindolin-1-ones
in moderate to good yields.
The chemistry of cyclopropenes has been explored exten-
1
3
2
sively. Cyclopropene derivatives – highly strained carbocyclic
molecules – have been shown to possess unique reactivity in
organic synthesis. Three typical reaction modes have been ob-
served in the chemistry of cyclopropenes, i.e. nucleophilic addi-
tion to the strained C=C bond, ring-opening rearrangement to an
allyl carbene and cycloadditions to the carbon-carbon double
bond. Several cycloaddition-based tandem ring-opening reac-
tions of cyclopropenes have also been investigated. However,
reactions of cyclopropenes with N-acyliminium cations have not
been studied as yet. N-Acyliminium cations are known as im-
portant reactive species in organic synthesis for the construction
of carbon-carbon bonds. Numerous examples of N-acyliminium
ion based intramolecular cyclizations can be found in the synthe-
sis of alkaloid derivatives. Recently, Wang, Zhang and Jha re-
ported the first examples of the Lewis acid catalyzed [4+2] cy-
cloaddition reactions of N-acyliminium ions with alkenes.
2
3
4
5
2. Results and discussion
6
The reaction of ethyl 2,3-diphenylcycloprop-2-ene-
carboxylate (1a) with 5-hydroxy-1-(p-tolyl)-1H-pyrrol-2(5H)-one
(2a) was first investigated in acetonitrile in the presence of
7
Yb(OTf) , Sc(OTf) or Sn(NTf ) and also in methylene dichlo-
3
3
2 4
ride in the presence of BF ·Et O, TiCl or AlCl (Table 1, Entries
3
2
4
3
8
1
–6). During the optimization of reaction conditions, it was
found that the Yb(OTf) , Sc(OTf) , Sn(NTf ) , TiCl and AlCl3
3
3
2 4
4
9
completely failed to yield the expected adduct 3, and only
BF ·Et O was able to produce adduct 3 in a 2.6:1 diastereomeric
10
In continuation of our earlier work, we have studied the re-
actions of substituted cyclopropenes with N-acyliminium cations.
In the present work we show for the first time that 2,3-
diphenylcycloprop-2-enecarboxylate, 2-methyl-3-phenylcyclo-
prop-2-enecarboxylate
—
3
2
mixture in 11% overall yield (Table 1, entry 3). The structure of
the major diastereomer 3 was confirmed unequivocally by X-ray
diffraction analysis (Fig. 1). The reaction 1a with 4 did not take
place in CH Cl in the precence of BF ·Et O and also in acetoni-
and
2,3,3-triphenylcycloprop-1-
2
2
3
2
——
trile in the presence of Yb(OTf)
3
(Table 1, entries 7 and 8). The
∗
Corresponding author. Tel: +7 812-428-4021; fax: +7-812-428-6939; e-mail: alstepakov@yandex.ru

2
Tetrahedron
reaction of 1a with 6a in anhydrous CH Cl at room tempera-
2
2
ACCEPTED MANUSCRIPT
a
Table 2. Reactions of cyclopropenes 1a–с with hydroxylactams 2a–c.
ture gave a diastereomeric mixture of 7a+8a in 41% overall yield
Table 1, entry 9). The same reaction at reflux condition results in
(
R1
sharp decrease in yield of 7a+8a (Table 1, entry 10). Of the Lew-
Ph
H
Ph
is acids and solvents screened, the combination of BF ·OEt and
3
2
dichloromethane produced the best results these reactions.
R2
N
a
Table 1. Optimisation of the reaction conditions.
OH
N
O
R1
3
BF
3
·Et
2
O
R2
or
+
CH
2
Cl2, RT
CO
2
Et
Ph
Ph
Ph
R1
O
Ph
H
1a-c
2b-c
OH
N
2
CO Et
H
Ph
LA
H
Me
N
Me
+
solvent, RT
R2
N
Ph
Ph
O
O
1a
2a
3
O
9
CO
2
Et
Ph
1
2
b
Ph
Entry
R
R
Product
Yield, %
OH
N
1
2
CO
CO
2
Et (1a)
Et (1a)
Me (2a)
H (2b)
3
−
11 c
2
CO Et
2
c.m.
LA
+
Me
N
Me
solvent, RT
3
4
5
CO Me (1b)
Cl (2c)
H (2a)
Me (2b)
9
−
−
9
c.m.
c.m.
2
Ph
Ph
c
O
O
Ph (1c)
Ph (1c)
1a
4
5 (not found)
CO Et
Ph
c
2
a
Reaction conditions: 1 (0.2 mmol), 2 (0.2 mmol), BF
mmol), CH
3
·Et
2
O (0.22
b
c
Ph
2
Cl
2
(5 mL), 16 h. Isolated yield. c.m. = complex mixture.
OH
N
H
2
CO Et
LA
+
Me
N
Me
solvent, RT
Ph
Ph
O
O
1a
6a
7
a+8a
Product b
Entry
Reactants
LA (equiv.)
Solvent
(
yield, %)
1
2
3
4
5
6
7
8
1a + 2a
1a + 2a
1a + 2a
1a + 2a
1a + 2a
1a + 2a
1a + 4
1a + 4
1a + 6a
1a + 6a
Yb(OTf)
Sc(OTf)
BF ·Et O (1.1)
TiCl (1.1)
Sn(NTf (0.03)
AlCl (1.1)
Yb(OTf) (0.3)
3
(0.3)
(0.2)
acetonitrile
acetonitrile
3 (trace)
n.r.
c
3
3
2
CH
CH
2
Cl
Cl
2
3 (11)
d
4
2
2
c.m.
2
)
4
acetonitrile
CH Cl
acetonitrile
3 (trace)
3 (trace)
3
2
2
c
3
n.r.
d
BF
BF
BF
3
·Et
·Et
·Et
2
2
2
O (1.1)
O (1.1)
O (1.1)
CH
CH
CH
2
2
2
Cl
2
Cl
2
Cl
2
c.m.
9
1
3
7a+8a (41)
7a+8a (25)
e
0
3
a
Reaction conditions: 1a (0.2 mmol), 2a, 4 or 6a (0.2 mmol), LA, solvent (5
b
c
d
mL), 16 h. Isolated yield. n.r. = no reaction. c.m. = complex mixture.
Fig. 1. X-ray structure of 3.
e
Reflux conditions.
Next experiment was performed with cyclopropene 1a and
hydroxylactam 2b in CH Cl (room temp. 16 h) in the presence
2
2
of BF ·Et O, affording an intractable reaction mixture (Table 2,
3
2
entry 2). Cyclopropene 1b was reacted with 2c in CH Cl at am-
2
2
bient temperature. After stirring for 12 h and extractive work up,
TLC analysis indicated the formation of several compounds. On-
ly methyl (1RS)-1-[(2SR)-1-(4-chlorophenyl)-5-oxo-2,5-dihydro-
1
H-pyrrol-2-yl]-2-phenyl-1H-indene-3-carboxylate (9) was iso-
lated from the reaction mixture by column chromatography in
% yield; no other products were isolated (Table 2, entry 3). The
9
relative stereochemistry of the formed stereocenters of pyrrol-
ylindene 9 was determined by single-crystal X-ray diffraction
and supported the relative configuration deduced from NMR
spectroscopy (Fig. 2). The triphenylcyclopropene 1c was then
used in the reactions. However, in these cases, only complex
mixtures of unidentified products were obtained (Table 2, entries
Fig. 2. X-ray structure of 9.
4
and 5).

3
propene ring). This fact indicated that H-C(11b) and methyl
ACCEPTED MANUSCRIPT
a
Table 3. Reactions of cyclopropenes 1a,b,d,e with hydroxylactams 2a–c.
group of cyclopropane ring are cis-located relative to each other
(see Supporting information).
R3
CO
2
Next, the reactions of diphenylcyclopropenes 1a,b with N-
acyliminium cations (generated from hydroxylactams 9a−g) were
investigated. Reaction of cyclopropene 1a with 6a in CH Cl
R1
R2
H
2
2
R4
N
(RT, 18 h) in the presence of BF ·OEt led to the formation of an
3 2
inseparable mixture of two diastereomers 7f and 8f in 29% over-
all yield (1:1 diastereomeric ratio were determined from H NMR
OR3
OH
N
O
O
1
7
a-i
BF
3
·Et
2
O
+
Ar
+
spectra by integration of the C11b-H signal) (Table 3, entry 7).
Recrystallization of a 1:1 mixture from methylene chlo-
ride/ethanol resulted in pure diastereomer 8f. The fused pentacy-
clic structure and relative stereochemistry of the 8f were con-
firmed by single-crystal X-ray diffraction (Fig. 5). Similarly, the
reaction of cyclopropene 1a with hydroxylactam 6b led to an
inseparable mixture of isoindoloquinolones 7a and 8a in 4:1 ra-
tio, respectively (Table 3, entry 8). Recrystallization of the mix-
ture 7a/8a from methylene chloride/ethanol gave pure sample of
7a. The structure of 7a was established unequivocally by X-ray
diffraction analysis (Fig. 3).
CH
2
Cl
2
R3
R1
R2
CO
2
O
1
a,b,d,e
6a-g
R1
R2
H
R4
N
O
8a,f-i
1
2
3
4
b
Entry
R
R
R
Ar
R
Yield, %
(product)
c
1
2
3
4
5
6
7
8
9
Me
Me
Me
Me
Me
Me
Ph
Me
Me
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Me (1d) Ph (6a)
Me (1d) 4-MeOC
H
n.r.
The reactions 1b with hydroxylactams 6c−g were then stud-
ied (CH Cl , BF ·OEt , RT, 18 h). The reaction of 1b with 6c
c
6
H
4
(6c)
(6c)
MeO
H
n.r.
2
2
3
2
Me (1e)
Me (1e)
Me (1e)
Me (1e)
Et (1a)
Et (1a)
Ph (6a)
4-Tol (6b)
4-MeOC
34 (7b)
38 (7c)
51 (7d)
53 (7e)
afforded a mixture of 7g and 8g (1.2:1 ratio) (Table 3, entry 9).
Recrystallization of the mixture 7g/8g from methylene chlo-
ride/methanol gave pure sample of 7g. The structure of 7g was
established unequivocally by X-ray diffraction analysis (Fig. 4).
The reactions of cyclopropene 1b with N-acyliminium cations
generated from hydroxylactams 6d,e gave chromatographically
inseparable mixtures of diastereomers 7h/8h and 7i/8i in total
yields 60% and 64%, respectively (Table 3, entries 10 and 11).
Recrystallization of the mixtures 7h/8h and 7i/8i from methylene
chloride/ethanol gave pure samples of 7h and 7i as single dia-
stereomers. The cyclopropa[c]isoindolo[2,1-a]quinolones 7/8
were obtained with increased yields by using hydroxylactams 6
with electron-donating groups (MeO, PhO, I) on the benzene ring
(Table 3, entries 5, 6, 9-11). Evidently, the electron-donating
substituents at the para position of the 2-phenyl group in 6c−e
increased the reactivity of benzene rings toward the intramolecu-
lar Friedel-Crafts reaction.
Me
MeO
PhO
H
6
H
4
4-PhOC
6
H
4
(6d)
d,e
d,f
Ph (6a)
29 (7f+8f)
Ph
4-Tol (6b)
Me
41(7a+8a)
d,f
d,f
Ph
Me (1b) 4-MeOC
Me (1b) 4-PhOC
Me (1b) 4-IC
Me (1b) 3-MeOC
Me (1b) 3-MeC
6
H
4
(6c)
MeO 54 (7g+8g)
1
1
1
1
0
1
2
3
Ph
6
H
4
(6d)
PhO 60 (7h+8h)
d,f
Ph
6
H
4
(6e)
I
64 (7i+8i)
c
Ph
6
H
4
(6f)
n.r.
Ph
6
H
4
(6g)
trace
a
Reaction conditions: 1 (0.8 mmol), 6 (0.8 mmol), BF
CH Cl (6 mL), 18 h, RT. Isolated yield. n.r. = no reaction. Chromato-
2 2
graphically inseparable mixture of two diastereomers [7f/8f (1:1), 7a/8a
4:1), 7g/8g (1.2:1), 7h/8h (4:1), 7i/8i (5:1) by H NMR data]. The 8f was
3
2
·Et O (0.9 mmol),
d
b
c
1
e
(
f
isolated in pure form by recrystallization. The diastereomer 7 was isolated
in pure form by recrystallization.
Unfortunately, only intractable fluorescent material formed
in the cases of 3-methoxyphenyl and 3-methylphenyl substituted
N-acyliminium ion precursors 6f and 6g (Table 3, entries 12 and
13). In both cases, the starting cyclopropene 1b was recovered
almost quantitatively. The formation of trace amount of isomeric
isoindoloquinolones S7 and S8 was observed in the reaction of
6g with cyclopropene 1b (see Supporting information).
For the next step in our study, we treated methyl 2,3-
dimethylcycloprop-2-enecarboxylate 1d with hydroxylactams 6a
and 6c (Table 3, entries 1 and 2). No reaction took place between
1
d and hydroxylactams 6a or 6c after prolonged stirring (20 h) in
the presence of BF ·Et O. No reaction was detected in this case
3
2
even under refluxing conditions. Under an argon atmosphere,
methyl 2-methyl-3-phenylcycloprop-2-enecarboxylate (1e) was
reacted with an equimolar amount of 6a in the presence of
BF ·OEt (1.1 equiv) in CH Cl at ambient temperature for 18 h,
3
2
2
2
to give methyl 11c-methyl-7-oxo-1a-phenyl-1a,7,11b,11c-
tetrahydro-1H-cyclopropa[c]isoindolo[2,1-a]quinoline-1-
carboxylate (7b) as a single diastereomer in 34% isolated yield
(
Table 3, entry 3). Although several other products could be seen
during the TLC analysis of the reaction mixture, no other poten-
tial products were successfully isolated. The reactions of cyclo-
propene 1e with hydroxylactames 6b−d were carried out in di-
chloromethane under similar conditions to those described previ-
ously (Table 3, entries 4-6). The reactions proceeded smoothly at
room temperature to give the cyclopropa[c]isoindolo[2,1-
a]quinolones 7c−e as single diastereomers in 41-53% yields. The
relative configuration of products 7b−e were determined on the
Fig. 3. X-ray structure of 7a.
1
basis of 2D NOESY H NMR spectrum of compound 7e. For
1
example, the H NMR spectrum of compound 7e displayed a
singlet at 4.80 ppm for H-C(11b), which showed a 2D-NOESY
correlation with a singlet at 1.85 ppm (CH group of the cyclo-
3

4
Tetrahedron
crystallization from methanol. The products 12a,b were fully
ACCEPTED MANUSCRIPT
1
13
characterized by H, C NMR and MS. Unfortunately, the reac-
tions of 11 (Ar = 4-Tol, 4-ClC H and 4-MeOC H ) with 1b led
6
4
6
4
to the formation of an inseparable complex mixtures, which made
1
products separation difficult (the H NMR spectra of reaction
mixtures were too complicated and it was impossible to identify
the single diastereomers). Isoindolobenzazepines 12' were not
obtained from these reactions.
Ar
OH
N
Ph
O
OMe
MeO
2
C
O
N
Ar
BF
3
·Et
2
O
Fig. 4. X-ray structure of 7g.
+
CH
2
Cl
2
Ph
Ph
O
1b
11a,b
1
2a, Ar = Ph, 56%
BF .
12b, Ar = 2,4-Cl
2
C
6
H
3
, 53%
3
Et
Cl
2
O
CH
2
2
2
MeO C
Ph
Ph
R
N
O
12'
Scheme 2. Reactions of cyclopropene 1a with hydroxylactams 11a,b.
Fig. 5. X-ray structure of 8f.
CO
2
Et
Ph
Next, we went on to explore the reactivity of another cyclo-
propene derivative 1c with hydroxylactams 6 and 11 under the
same reaction conditions (Table 4). The reaction of 1c with hy-
droxylactam 6b at room temperature for 16 h gave 3-(1,2-
diphenyl-1H-inden-3-yl)-2-(4-methylphenyl)isoindolin-1-one
(13a/14a) as an inseparable mixture of two diastereomers in 59%
overall yield (Table 4, entry 2). It should be noted that the yield
did not improve upon stirring the reaction for a longer period of
Ph
N
Cl
OH
O
CO
Et
O
2
7j/8j
BF
3
·Et
2
O
+
N
Cl
+
CH
2
Cl2, RT
Ph
Ph
O
CO
Ph
2
Et
time or at
a
higher temperature. 2-(4-Chlorophenyl)-3-
1
a
6h
hydroxyisoindolin-1-one (6b) also underwent the reaction
smoothly with 1c to give the desired isomeric indene adducts
1
3b/14b (Table 4, entry 3). Similarly, reaction 1c with hydrox-
ylactams 7c−d, in all cases, lead to mixtures of the diastereomers
3c−e and 14c−e in overall yields ranging from 60% to 74% (Ta-
N
Cl
O
10
1
ble 4, entries 4-6). The products of the reactions were isolated by
preparative thin layer chromatography on silica gel. Recrystalli-
zation of the mixtures 13d/14d and 13e/14e from metha-
nol/CH Cl gave pure major diastereomers 13d and 13e. The
relative stereochemistry of the formed stereocenters of major
diastereomers 13 was determined by single-crystal X-ray diffrac-
tion (for compounds 13a and 13d) (Fig. 6 and 7). The reactions
of hydroxylactams 6a and 11a with 1c led to complex mixtures
Scheme 1. Reactions of cyclopropene 1a with hydroxylactam 6h.
For the next step in our study, we treated cyclopropene 1a
with hydroxylactam 6h (Ar = 4-ClC H ) (Scheme 1). The reac-
2
2
6
4
tion proceeded at room temperature producing the 7j/8j and 10.
Compounds 7j/8j and 10 were obtained as a 2:1 inseparable mix-
ture in 32% overall yield. Evidently, the electron-withdrawing
group at the para position of the 2-phenyl group in 6h decreased
the reactivity of the aryl group in the intramolecular Friedel-
Crafts reaction. In this case, the reaction proceeds via two ways:
(
Table 4, entries 1 and 7). It should be noted that 1,2,3-
triphenylcyclopropenylium tetrafluoroborate (17) was isolated as
the by-product in all the cases of the reactions with 1,2,3-
triphenylcyclopropene (1c) (see below).
1
) via the intramolecular Friedel-Crafts reaction with formation
of isoindoloquinolone 7j/8j and 2) through the stage of cyclo-
propane rearrangement with formation of isoindolinindene 10.
We further explored the scope of the reaction by replacing
the 2-aromatic substituent with a benzyl group. The reactions of
1
b with N-acyliminium ion precursors 11a,b were investigated
(Scheme 3). Under an argon atmosphere, compound 1b was re-
acted with an equimolar amount of 11a in the presence of
BF ·OEt in CH Cl at ambient temperature to give methyl 3-(2-
3
2
2
2
benzyl-1-oxoisoindolin-3-yl)-2-phenyl-1H-indene-1-carboxylate
12a) as a 3:1 diastereomeric mixture in 56% overall yield. Re-
(
crystallization of the 3:1 mixture from methanol gave pure major
diastereomer. Similarly, reaction of 1b with 11b lead to indene
Fig. 6. X-ray structure of 13a.
1
2b as a 2:1 mixture of isomers in 53% overall yield. The dia-
stereomers proved to be inseparable by column chromatography.
However, the major isomer was isolated from the 2:1 mixture by

5
a
a
Table 4. Reactions of cyclopropene 1c with hydroxylactams 6a–e,h; 11a.
Table 5. Reactions of cyclopropenes 1f−h with hydroxylactams 6b,с.
ACCEPTED MANUSCRIPT
Ph R2
Ph
R
Ph R2
Ph
H
R1
O
Ph
H
N
OH
N
CO
Ph
2
Me
H
R1
Ph
1
f-h
·Et
CH Cl
Ar
N
O
R
3
P
+
BF
3
2
O
OH
N
Ph
2
2
O
1
3a-e
BF
3
·Et
2
O
6b,c
16
1
5a,b
+
R
+
CH
2
Cl
2
Ph
R
Ph
Ph
Ph
Entry R1
R2
Ar
R3
Yield, %
product)
O
O
H
N
b
H
(
1c
6a-e,h; 11a
c
1
2
3
4
Ph
Ph
CO
CO
Me (1f)
HC(COMe)
Me Ph (1h)
Me Ph (1h)
4-MeOC
(1g) 4-MeOC
6
6
H
4
(6c)
(6c)
c.m.
62
d
2
H
4
e
2
4-MeC
6
H
4
(6b)
Me 18 (15a)f
14a-e
2
4-MeOC
6
H
4
(6c) MeO 24 (15b)
a
Reaction conditions: 1 (0.2 mmol), 6 (0.2 mmol), BF
3
·Et
2
O (0.22
b
d
b
c
Entry
R
Product (yield, %)
c.m.
Ratio of 13/14
mmol), CH
2
Cl
2
(5 mL), 18 h, RT. Isolated yield. c.m. = complex
mixture. 1,2,3-Triphenylcyclopropenylium tetrafluoroborate (17) was
isolated as single product. Indene 16 was isolated in 19% yield as the
by-product. Indene 16 was isolated in 17% yield as the by-product.
c
d
1
2
3
4
5
6
7
Ph (6a)
4-Tol (6b)
4-ClC (6h)
4-IC (6e)
4-MeOC
4-PhOC
Bn (11a)
−
3.4:1
e
e
13a/14a (59)
13b/14b (66)
13c/14c (74)
13d/14d (60)
13e/14e (65)
f
6
H
4
3.7:1
4.0:1
6
H
4
f
6
H
4
(6c)
(6d)
4.6:1
3.0:1
g
6
H
4
c
c.m.
−
a
Reaction conditions: 1 (0.2 mmol), 2 (0.2 mmol), BF
3
·Et
2
O (0.22d
b
c
mmol), CH
2
Cl
2
(5 mL), 16 h. Isolated yield. c.m. = complex mixture.
1
e
Determined by H NMR analysis of the crude reaction product. The 13a
f
was isolated in pure form by recrystallization from CH
3d was isolated in pure form by recrystallization from CH
The 13e was isolated in pure form by recrystallization from
CH Cl /MeOH.
2 2
Cl /MeOH. The
g
1
2 2
Cl /MeOH.
2
2
Fig. 8. X-ray structure of 15b.
a
3 2
Table 5. Reactions of cyclopropenes 1g,i,j with BF ·Et O.
R1
O
R2
Ph
Ph
.
BF Et O
3
2
BF4
O
+
CH Cl
2
2
Ph
Ph
Ph
Ph
Fig. 7. X-ray structure of 13d.
1g,i,j
17
b
Entry
R1
R2
Yield of 17, %
We also examined the reaction of sterically hindered 3,3-
disubstituted cyclopropenes 1f−h with hydroxylactams 6b,c. The
reaction of 1,2,3-triphenyl-3-methylcyclopropene with 6c led to a
complex mixture (Table 5, entry 1). At the same conditions
1
2
3
Me
Me
Me
Me (1g)
Ph (1i)
87
89
81
CO
2
Et (1j)
a
Reaction conditions: 1 (0.2 mmol), BF
mL), 18 h, RT. Isolated yield.
3
·Et
2
O (0.24 mmol), CH
Cl
2 2
(5
b
(
CH Cl , BF ·Et O, RT), tetrasubstituted cyclopropene 1g does
2 2 3 2
not react with hydroxylactam 6c and only 1,2,3-
triphenylcyclopropenylium tetrafluoroborate (17) was isolated as
single product in 62% yield (Table 5, entry 2). In the reactions of
the hydroxylactams 6b,c with unsymmetrically substituted me-
thyl 2,3,3-triphenylcycloprop-1-enecarboxylate (1h), the adducts
Since we have an interesting and unexpected result – the
formation of 1,2,3-triphenylcyclopropenylium tetrafluoroborate
(17) in all the cases we used cyclopropenes with three phenyl
substituents – we decided to study the interaction of some cyclo-
propenes with BF ·Et O. As the test experiments, we treated cy-
3
2
1
5a and 15b were formed in 18 and 24% yield, respectively (Ta-
clopropenes 1g,i,j with BF ·Et O. We found that if cyclopro-
3
2
ble 5, entries 3 and 4). The structure of compounds 15 was con-
1
penes 1g,i,j were allowed to react with 1.2 equiv of BF
·Et O
3 2
firmed by H NMR data and X-ray crystal analysis (for com-
(
CH Cl , RT), in all cases cyclopropenylium cation 17 was ob-
2
2
pound 15b) (Fig. 8). Observed diastereoselectivity corresponds to
the preferential attack of the molecule of N-acyliminium cation
on C1-atom of the cyclopropene 1h. Methyl 2,3-diphenyl-1H-
indene-1-carboxylate (16) was isolated in 17−19% yields as the
by-product in all the cases of the reactions with methyl 2,3,3-
triphenylcycloprop-1-enecarboxylate (1h).
tained in 81-89% yield (Table 5). The structure of this salt was
determined by X-ray crystallography (Fig. 9). Single crystals of
1
,2,3-triphenylcyclopropenylium tetrafluoroborate (17) adequate
for the X-ray analysis were crystallized from CH Cl .
2
2

6
Tetrahedron
little effect on fluorescence quantum yields of 7. For example,
ACCEPTED MANUSCRIPT
among the isoindoloquinolones 7a,h-i the methoxy and phenoxy
substituted 7g and 7h has higher fluorescence quantum yields
than the 7a and 7i substituted by weak electron-donating groups
(
Table 6, entries 1–4). Similarly, the fluorescence quantum yields
of the methoxy substituted inden-isoindolinone 13d are higher
than the methyl substituted 13a (Table 6, entries 10 and 11).
Table 6. Optical properties of 7a,h-i, 8f, 12a,b, 13a,d in dichloro-
methane.
Entry
a
Compound
λabs (nm)
331
λem (nm)
434
Φ
F
Figure 9. X-ray structure of 17.
1
2
3
4
5
6
7a
7g
7h
7i
8f
12a
12a
12b
12b
13a
13d
0.03
0.05
0.04
0.03
0.02
0.37
0.41
0.42
0.48
0.04
0.06
330
330
330
331
331
299
331
299
450
441
420
414
382
380
381
416
BF
3
·Et
2
O
6
N
Ar
1
8
O
R2
b
7
R1
8
Ph
1
R2
b
9
Ph
R2
R1
10
11
330
331
445
464
R1
H
Ph
H
a
Ar
N
+
N
Ar
O
Absolute quantum yield was determined by a calibrated integrating
b
sphere system. Solid-state (KBr pellets).
O
R2
R1
R1
The highest quantum yields were observed for 3-(2-benzyl-
1-oxoisoindolin-3-yl)-2-phenyl-1H-indene-1-carboxylates 12a,b
containing an electron withdrawing substituent at position 1 of
the indene moiety and the benzyl substituent on the phenylisoin-
Ph
R2
H
Ph
Ph
H
R1 = R2 = Ph
H
H
Ar
O
+
N
Ph
Ar
N
Ar
cyclopropyl-allyl
rearrangement
N
O
R1 = Me, Ph;
2
20
dolinone nitrogen [Φ = 0.37 (in CH Cl ) and 0.41 (in KBr) for
19
F 2 2
R
= CO
2
Alk
21
O
1
2a and Φ = 0.42 (in CH Cl ) and 0.48 (in KBr) for 12b]. The
F 2 2
intramolecular
Friedel-Crafts
reaction
intramolecular
Friedel-Crafts
reaction
fluorescence spectra of 12a,b exhibit the following spectral fea-
tures: (1) 12a shows a fluorescence maximum at 382 nm (in
CO
2
R3
CO R
2
3
Ph
R1
R2
R1
R2
CH Cl ) and 380 nm (in KBr); (2) 12b exhibit fluorescence max-
2 2
H
H
Ph
Ar
imum located at 381 nm (in CH Cl ) and 416 nm (in KBr). It is
2 2
surprising that the values of the quantum yields of 3-(2-benzyl-1-
oxoisoindolin-3-yl)-2-phenyl-1H-indene-1-carboxylates 12a,b
R4
R4
N
N
N
O
O
7
8
O
(Φ = 0.37-0.48) is almost an order of magnitude greater than the
F
1
3+14
values of quantum yields of 3-(1,2-diphenyl-1H-inden-3-yl)-2-
arylisoindolin-1-ones 13a,b (ΦF = 0.04-0.06). Increasing the
quantum efficiency (12>13), most likely determined by the na-
ture of the substituents at position 1 of the indene moiety and
substituents on the phenylisoindolinone nitrogen.
Scheme 3. A possible pathways for the reactions of hydroxylactams 6 with
cyclopropenes 1.
9
10
Based on literature reports and our previous work, a plau-
sible mechanism is shown in Scheme 3. The initial dehydroxyla-
tion produces an N-acyliminium cation 18 followed by electro-
3
. Conclusion
In summary, we have reported for the first time the reac-
philic attack on the double bound of cyclopropene, leading to a
2
carbocations 19 and 20. In that case, if the R = CO Alk, subse-
2
quent the intramolecular Friedel-Crafts reaction of the cations 19
and 20 leads to the cyclopropa[c]isoindolo[2,1-a]quinolones 7
tions of cyclopropenes with N-acyliminium cations, generated
from hydroxylactams. It is shown that 2,3-diphenylcycloprop-2-
enecarboxylate, 2-methyl-3-phenylcycloprop-2-enecarboxylate
and 2,3,3-triphenylcycloprop-1-enecarboxylate react with N-
acyliminium cations generated from 3-hydroxy-2-arylisoindolin-
1
2
and 8, respectively. In case R = R = Ph, cations 19 and 20 un-
dergoes a cyclopropyl–allyl rearrangement to give cation 21. The
cation 21 undergoes cyclization to give substituted indenes 13
and 14. Clearly, the steric factors are favorable to the addition of
the N-acyliminium cations to the cyclopropenes from the less
sterically hindered side.
1
-ones in the presence of BF ·OEt to give the corresponding
3 2
cyclopropa[c]isoindolo[2,1-a]quinolones in moderate yields. The
reaction of N-acyliminium cations with 1,2,3-triphenylcycloprop-
We
have
found
that
cyclopropa[c]isoindolo[2,1-
1
-ene proceed smoothly at room temperature to afford 3-(1H-
a]quinolones 7,8 and 3-(1H-inden-3-yl)isoindolin-1-ones 12,13
are fluorescent compounds. Compounds 7a,h-i, 8f, 12a,b, 13a,d
showed blue emissions (λem = 381-464 nm) in dichloromethane
inden-3-yl)isoindolin-1-ones in moderate to good yields. Both
cyclopropa[c]isoindolo[2,1-a]quinolones and 3-(1H-inden-3-
yl)isoindolin-1-ones are fluorescent compounds that showed blue
emissions (λem = 381-517 nm) in dichloromethane with low to
with low to moderate fluorescence quantum yields (Φ = 0.02-
F
0
.42) as summarized in Table 6. Fluorescence of the compounds
moderate fluorescence quantum yields (Φ = 0.02-0.48). These
F
7
, 8, 12, 13 probably occurs due to the presence in their struc-
compounds may be of interest for medicinal and materials sci-
ence.
This study provides not only an unique approach to novel
polycyclic systems, which are not easily accessible by other
methods, but also offers a new synthetic pathway to complex
11
tures of N-phenylisoindolinone fragment.
As shown in Table 6, the maximum absorption wavelengths
(
λabs) and emission wavelengths (λ ) of 7a,h-i and 8f were in the
em
range of 330–331 nm and 414–450 nm, respectively. It should be
noted that the substituents on aryl group at nitrogen atom has

7
molecular skeletons. Extension of this strategy to other substrates
is under the way in this laboratory.
J = 8, 1 Hz, 1 H, Harom.), 7.18–7.30 (m, 5 H, Harom.), 7.37 (t, J =
ACCEPTED MANUSCRIPT
7 Hz, 1 H, H ), 7.46–7.53 (m, 2 H, Harom.), 7.55–7.61 (m, 1 H,
Harom.), 7.92–8.01 (m, 3 H, Harom.). C NMR (100 MHz, CDCl ) δ
arom.
13
3
1
4
1
1
3.9 (CO CH CH ), 21.3 (Me), 30.3 (CHcycloprop.), 42.9 (Ccycloprop.),
2 2 3
4
4
. Experimental section
8.9 (Ccycloprop.), 60.7 (CO CH CH ), 61.9 (CH), 122.0, 123.9,
2
2
3
24.5, 127.3, 127.4, 127.5, 127.9, 128.0, 128.2 (2C), 128.9,
30.1, 130.6, 131.6, 131.9, 132.2, 132.3, 132.4, 133.4, 133.5,
.1. General remarks
All reactions were performed in anhydrous solvents under
134.0, 134.2, 134.4, 141.4, 166.8 (CO), 169.0 (CO). HRMS
(ESI): calcd. for С33Н27NNaO [M+Na] 508.1884; found
3
508.1877.
+
an argon atmosphere. Dichloromethane was dried over CaH and
2
distilled prior to use. Hexane and ethyl acetate for the chromatog-
raphy were distilled before use. The IR spectra were measured on
a Bruker Tensor 27 spectrophotometer. Melting points were de-
4.2.2. (1SR,1aRS,11bRS,11cRS)-Methyl 11c-methyl-7-oxo-1a-
phenyl-1a,7,11b,11c-tetrahydro-1H-cyclopropa[c]isoindolo[2,1-
a]quinoline-1-carboxylate (7b). Obtained as single diastereomer
using general procedure from hydroxylactam 6a (180 mg, 0.8
1
13
termined on a Boetius instrument and are uncorrected. H and
C
NMR spectra were recorded in CDCl using a Bruker DPX–300
3
spectrometer or a Bruker Avance 400. Chemical shifts are report-
1
13
ed relative to CDCl ( H: δ = 7.26 ppm; C: δ = 77.0 ppm). Inte-
mmol), cyclopropene 1e (151 mg, 0.8 mmol) and BF
mL, 0.9 mmol) in 34% yield (108 mg). R 0.37 (3:1 hex-
anes:EtOAc), white solid, m.p. 204–206 ºС. IR (KBr) ν 909,
3 2
⋅OEt (0.11
3
grals are in accordance with assignments; coupling constants are
f
13
given in Hz. All C NMR spectra are proton-decoupled. Multi-
plicity is indicated as follows: s (singlet), d (doublet), t (triplet), q
max
1
1162, 1372, 1490, 1599, 1689, 1720, 2951, 3026, 3061. H NMR
(quartet), m (multiplet), dd (doublet of doublet). The X-ray dif-
(400 MHz, CDCl ) δ 1.84 (s, 3 H, Me), 2.29 (s, 1 H, CHcycloprop.),
3
fraction data were performed by means of a Bruker APEX-II
CCD diffractometer with Mo-K X-ray radiation. HRMS spectra
were obtained with a Bruker-micrоTOF and a Bruker-maXis
3.55 (s, 3 H, CO Me), 4.80 (s, 1 H, CH), 6.57 (d, J = 8 Hz, 1 H,
Harom.), 6.98 (t, J = 7 Hz, 1 H, Harom.), 7.13 (d, J = 7 Hz, 1 H,
Harom.), 7.24–7.33 (m, 2 H, Harom.), 7.41–7.49 (m, 3 H, Harom.),
2
(
QTOF). Reactions were monitored by TLC analysis using Silu-
7.59–7.68 (m, 2 H, H ), 7.79 (d, J = 8 Hz, 1 H, Harom.), 8.00 (d,
arom.
1
3
fol UV-254 plates. Thin layer chromatography was performed on
silica gel 5−40 mesh eluted with ethyl acetate/hexane. Crystallo-
graphic data have been deposited at the Cambridge Crystallo-
graphic Data Centre [Deposition No. CCDC-1471342 (3),
CCDC-1471341 (7a), CCDC-1471640 (7g), CCDC-1471639
J = 2 Hz, 2 H, Harom.). C NMR (100 MHz, CDCl ) δ 16.1 (Me),
3
30.3 (CHcycloprop.), 38.3 (Ccycloprop.), 41.5 (Ccycloprop.), 51.6 (CO Me),
2
60.1 (CH), 122.3, 124.0, 124.5, 124.8, 127.0, 127.8, 128.3, 128.9,
129.0, 129.4, 131.6, 132.1, 132.3, 132.4, 132.5, 132.9, 134.9,
142.3, 166.8 (CO), 169.7 (CO). HRMS (ESI): calcd. for
+
(8f), CCDC-1471690 (9), CCDC-1471562 (13a), CCDC-
C
26
H
21NNaO
3
[M+Na] 418.1414; found 418.1416.
1
and
471563 (13d), CCDC-1471772 (15b), CCDC-1471689 (17)]
can
be
obtained
free
of
charge
via
and
4.2.3. (1SR,1aRS,11bRS,11cRS)-Methyl 3,11c-dimethyl-7-oxo-
1a-phenyl-1a,7,11b,11c-tetrahydro-1H-cyclopropa[c]isoindo-
lo[2,1-a]quinoline-1-carboxylate (7c). Obtained as single dia-
stereomer using general procedure from hydroxylactam 6b (191
mg, 0.8 mmol), cyclopropene 1e (151 mg, 0.8 mmol) and
9
a,c,12
www.ccdc.cam.ac.uk/data_request/cif. Hydroxylactams
cyclopropenes were prepared following known procedures.
13
4
.2. General procedure for the synthesis of cyclopro-
pa[c]isoindolo[2,1-a]quinolone derivatives.
BF ⋅OEt (0.11 mL, 0.9 mmol) in 38% yield (124 mg). R 0.35
3 2 f
(3:1 hexanes:EtOAc), white solid, m.p. 241–242 ºС. IR (KBr)
To a solution of the cyclopropene 1a, 1b, 1e, 1h (0.8
mmol) and hydroxylactam 6a–e (0.8 mmol) in anhydrous meth-
ylene dichloride (6 mL) under an argon atmosphere was added at
room temperature BF ⋅OEt (0.11 mL, 0.9 mmol) at one portion
νmax 928, 1151, 1213, 1369, 1433, 1504, 1612, 1703, 1739, 2855,
1
2950, 3040. H NMR (400 MHz, CDCl ) δ 1.82 (s, 3 H,
3
Mecycloprop.), 2.17 (s, 3 H, Me), 2.26 (s, 1 H, CHcycloprop.), 3.54 (s, 3
3
2
H, CO Me), 4.77 (s, 1 H, CH), 6.36 (s, 1 H, Harom.), 7.13 (t, J = 8
2
with stirring. After continued stirring at room temperature for 18
h (monitored by TLC), the solvent was removed under reduced
pressure. The residue was subjected to silica gel chromatography
Hz, 2 H, Harom.), 7.24 (d, J = 8 Hz, 1 H, Harom.), 7.42–7.47 (m, 3
H, Harom.), 7.59–7.67 (m, 2 H, Harom.), 7.78 (d, J = 8 Hz, 1 H,
Harom.), 7.90 (d, J = 8 Hz, 1 H, Harom.), 8.01 (d, J = 8 Hz, 1 H,
13
(3:1 hexanes:ethyl acetate) to give the products 7a–i, 8a,f–i, 15a–
Harom.). C NMR (100 MHz, CDCl ) δ 16.2 (Mecyclorop.), 21.2
3
b as summarized in Tables 3 and 5.
(Me), 30.4 (CHcycloprop.), 38.2 (Ccycloprop.), 41.5 (Ccycloprop.), 51.6
(
CO Me), 60.1 (CH), 122.2, 124.0, 124.4, 127.6, 127.7, 128.2,
2
4
.2.1. (1SR,1aRS,11bRS,11cSR)-Ethyl 3-methyl-7-oxo-1a,11c-
128.9, 129.0, 129.8, 130.1, 131.6, 132.1, 132.3, 132.4, 132.7,
134.5, 134.9, 142.3, 166.7 (CO), 169.7 (CO). HRMS (ESI):
diphenyl-1a,7,11b,11c-tetrahydro-1H-
cyclopropa[c]isoindolo[2,1-a]quinoline-1-carboxylate (7a) and
+
calcd. for C H NO [M+H] 410.1751; found 410.1750.
27
24
3
(1SR,1aRS,11bSR,11cSR)-ethyl 3-methyl-7-oxo-1a,11c-diphenyl-
1
a,7,11b,11c-tetrahydro-1H-cyclopropa[c]isoindolo[2,1-
4.2.4. (1SR,1aRS,11bRS,11cRS)-Methyl 3-methoxy-11c-methyl-7-
oxo-1a-phenyl-1a,7,11b,11c-tetrahydro-1H-cyclopropa[c]iso-
indolo[2,1-a]quinoline-1-carboxylate (7d). Obtained as single
diastereomer using general procedure from hydroxylactam 6c
(204 mg, 0.8 mmol), cyclopropene 1e (151 mg, 0.8 mmol) and
BF ⋅OEt (0.11 mL, 0.9 mmol) in 51% yield (173 mg). R 0.27
a]quinoline-1-carboxylate (8a). Obtained as a 4:1 diastereomeric
mixture using general procedure from hydroxylactam 6b (191
mg, 0.8 mmol), cyclopropene 1a (211 mg, 0.8 mmol) and
BF ⋅OEt (0.11 mL, 0.9 mmol) in 41% overall yield. Recrystalli-
3
2
zation of the 4:1 mixture from ethanol/CH Cl gave pure major
2
2
3
2
f
diastereomer 7a. Data for major diastereomeor 7a: R 0.41 (3:1
(3:1 hexanes:EtOAc), white solid, m.p. 221–223 ºС. IR (KBr)
f
hexanes:EtOAc), white solid, m.p. > 260 ºС. IR (KBr) νmax 904,
νmax 1076, 1157, 1223, 1285, 1404, 1506, 1613, 1683, 1736,
1
1
1
047, 1099, 1166, 1306, 1382, 1446, 1506, 1604, 1714, 2980. H
2835, 2944, 3004, 3060. H NMR (400 MHz, CDCl ) δ 1.83 (s, 3
3
NMR (400 MHz, CDCl ) δ 1.10 (t, J = 7 Hz, 3 H, CO CH CH ),
H, Me), 2.27 (s, 1 H, CHcycloprop.), 3.54 (s, 3 H,CO Me), 3.63 (s, 3
3
2
2
3
2
2
.18 (s, 3 H, Me), 2.75 (s, 1 H, CHcycloprop.), 3.88–3.96 (m, 1 H,
H, MeO), 4.76 (s, 1 H, CH), 6.13 (s, 1 H, Harom.), 6.85 (d, J = 8
Hz, 1 H, Harom.), 7.13 (s, 1 H, Harom.), 7.24 (d, J = 8 Hz, 1 H,
Harom.), 7.30–7.49 (m, 3 H, Harom.), 7.59–7.65 (m, 2 H, Harom.),
7.77 (d, J = 8 Hz, 1 H, Harom.), 7.92 (d, J = 8 Hz, 1 H, Harom.), 8.00
CO CH CH ), 4.03–4.11 (m, 1 H, CO CH CH ), 5.13 (s, 1 H,
CH), 5.82 (d, J = 8 Hz, 1 H, Harom.), 6.32 (s, 1 H, Harom.), 6.89 (d,
J = 8 Hz, 1 H, Harom.), 7.05 (dd, J = 7, 1 Hz, 1 H, Harom.), 7.17 (dd,
2
2
3
2
2
3

8
Tetrahedron
13
-1 1
(
d, J = 8 Hz, 1 H, Harom.). C NMR (100 MHz, CDCl ) δ 16.1
1681, 1708, 1738, 2944, 3374 cm . H NMR (400 MHz, CDCl
ACCEP
3
TED MANUSCRIPT
3,
(Me), 30.3 (CHcycloprop.), 38.1 (Ccycloprop.), 41.6 (C
), 51.6
for major diastereomer 7g) δ 2.82 (s, 1 Н, CHcycloprop.), 3.72 (s, 3
cycloprop.
(
CO Me ), 55.3 (MeO), 60.2 (CH), 111.5, 115.9, 123.4, 123.9,
Н, CO Me), 3.83 (s, 3 Н, MeO), 4.73 (s, 1 Н, СН), 6.85-6.94 (m,
2
.
2
1
1
24.3, 125.9, 127.9, 128.3, 128.9, 129.0, 131.6, 132.0, 132.2,
4 Н, Harom.), 7.05–7.15 (m, 5 Н, Harom.), 7.21–7.33 (m, 4 Н,
Harom.), 7.37 (d, J = 8 Hz, 1 H, Harom.), 7.58 (d, J = 8 Hz, 1 H,
32.5, 134.4, 134.7, 142.3, 156.6, 166.7 (CO), 169.6 (CO).
+
HRMS (ESI): calcd. for C H NO [M+H] 426.1700; found
4
Harom.), 7.80 (d, J = 8 Hz, 1 H Harom.), 8.12 (d, J = 8 Hz, 1 H,
27
24
4
1
26.1705.
Harom.). H NMR (400 MHz, CDCl for minor diastereomer 8g) δ
3,
2
.77 (s, 1 Н, CHcycloprop.), 3.55 (s, 3 Н, CO Me), 3.66 (s, 3 Н,
2
4
.2.5. (1SR,1aRS,11bRS,11cRS)-Methyl 11c-methyl-7-oxo-3-
MeO), 5.13 (s, 1 Н, СН), 5.83 (d, J = 8 Hz, 1 H Harom.), 6.07 (d, J
= 2 Hz, 1 H, Harom.), 6.85–6.94 (m, 3 Н, Harom.), 7.05–7.15 (m, 4
Н, Harom.), 7.21–7.33 (m, 3 Н, Harom.), 7.47 (d, J = 8 Hz, 1 H,
phenoxy-1a-phenyl-1a,7,11b,11c-tetrahydro-1H-cyclopro-
pa[c]isoindolo[2,1-a]quinoline-1-carboxylate (7e). Obtained as
single diastereomer using general procedure from hydroxylactam
H
arom.), 7.51 (d, J = 8 Hz, 1 H, Harom.), 7.90–8.01 (m, 3 Н, Harom.).
1
3
6
d (254 mg, 0.8 mmol), cyclopropene 1e (151 mg, 0.8 mmol)
C NMR (100 MHz, CDCl , 1.2:1 diastereomeric mixture) δ
3
and BF ⋅OEt (0.11 mL, 0.9 mmol) in 53% yield (207 mg). R
29.9, 40.0, 42.0, 42.6, 43.0, 48.8, 51.7, 52.0, 55.2, 55.4, 61.9,
70.0, 111.9, 113.3, 116.1, 116.2, 121.8, 123.2, 123.3, 123.9,
124.5, 124.7, 126.4, 126.7, 127.0, 127.4, 127.5, 127.6, 127.9,
128.1, 128.3, 128.5, 128.9, 130.9, 131.2, 131.5, 131.9, 132.1,
132.2, 132.3, 132.4, 133.2, 133.3, 133.7, 133.9, 134.7, 135.1,
3
2
f
0
.36 (3:1 hexanes:EtOAc), white solid, m.p. 231–232 ºС. IR
(
1
KBr) νmax 934, 1071, 1161, 1222, 1268, 1392, 1488, 1593, 1691,
735, 2947, 3055. H NMR (400 MHz, CDCl ) δ 1.85 (s, 3 H,
3
1
Me), 2.32 (s, 1 H, CHcycloprop.), 3.56 (s, 3 H, CO Me), 4.80 (s, 1 H,
2
CH), 6.30 (d, J = 4 Hz, 1 H, Harom.), 6.87–6.92 (m, 3 H, Harom.),
137.2, 141.3, 141.9, 156.5, 156.6, 165.2, 166.8, 169.5, 170.5.
+
7
.06–7.09 (m, 2 H, Harom.), 7.23–7.45 (m, 6 H, Harom.), 7.59–7.68
HRMS (ESI): calcd. for С32
Н26NO
4
[M+H] 488.1857; found
(
1
m, 2 H, Harom.), 7.78 (d, J = 7 Hz, 1 H, H ), 7.94 (d, J = 8 Hz,
H, Harom.), 8.00 (d, J = 7 Hz, 1 H, Harom.). C NMR (100 MHz,
488.1860.
arom.
1
3
CDCl ) δ 16.1 (Me), 30.4 (CHcycloprop.), 38.3 (Ccycloprop.), 41.5 (Ccy-
4.2.8.
(1SR,1aRS,11bRS,11cSR)-Methyl
7-oxo-3-phenoxy-
3
cloprop.), 51.7 (CO Me), 60.2 (CH), 117.0, 118.7 (2C), 120.3,
1a,11c-diphenyl-1a,7,11b,11c-tetrahydro-1H-
2
1
(
1
23.2, 123.5, 124.0, 124.4 (2C), 127.9, 128.4, 129.0, 129.1, 129.7
2C), 131.5, 131.9, 132.3, 132.4, 134.5, 134.8, 142.2, 154.0,
56.9, 166.8 (CO), 169.5 (CO). HRMS (ESI): calcd. for
cyclopropa[c]isoindolo[2,1-a]quinoline-1-carboxylate (7h) and
(1SR,1aRS,11bSR,11cSR)-methyl 7-oxo-3-phenoxy-1a,11c-diphe-
nyl-1a,7,11b,11c-tetrahydro-1H-cyclopropa[c]isoindolo[2,1-
a]quinoline-1-carboxylate (8h). Obtained as a 4:1 diastereomeric
mixture using general procedure from hydroxylactam 6d (254
mg, 0.8 mmol), cyclopropene 1b (200 mg, 0.8 mmol) and
+
C H NNaO [M+Na] 510.1676; found 510.1688.
32
25
4
4
.2.6. (1SR,1aRS,11bRS,11cSR)-Ethyl 7-oxo-1a,11c-diphenyl-
1
a,7,11b,11c-tetrahydro-1H-cyclopropa[c]isoindolo[2,1-a]qui-
BF
zation of the 4:1 mixture from ethanol/CH
diastereomer 7h. Data for major diastereomer 7h: R
3
⋅OEt
2
(0.11 mL, 0.9 mmol) in 60% overall yield. Recrystalli-
Cl gave pure major
0.30 (3:1
noline-1-carboxylate (7f) and (1SR,1aRS,11bSR,11cSR)-ethyl 7-
oxo-1a,11c-diphenyl-1a,7,11b,11c-tetrahydro-1H-cyclopro-
pa[c]isoindolo[2,1-a]quinoline-1-carboxylate (8f). Obtained as a
2
2
f
hexanes:EtOAc), white solid, m.p. 244–245 ºС. IR (KBr) νmax
1
:1 diastereomeric mixture using general procedure from hy-
droxylactam 6a (180 mg, 0.8 mmol), cyclopropene 1a (211 mg,
.8 mmol) and BF ⋅OEt (0.11 mL, 0.9 mmol) in 29% overall
938, 1063, 1099, 1159, 1213, 1264, 1387, 1446, 1488, 1589,
1
1694, 1744, 3027. H NMR (400 MHz, CDCl ) δ 2.84 (s, 1 H,
3
0
CHcycloprop.), 3.81 (s, 3 H, CO
Me), 4.77 (s, 1 H, CH), 6.80–7.55
2
3
2
yield. Recrystallization of the 1:1 mixture from ethanol/CH Cl2
gave pure single diastereomer 8f. Data for diastereomer 8f: Rf
(m, 20 H, Harom.), 7.80 (d, J = 7 Hz, 1 H, Harom.), 8.18 (d, J = 9 Hz,
1 H, Harom.). C NMR (100 MHz, CDCl ) δ 40.0 (Ccycloprop.), 41.9
3
2
13
0
(
1
.37 (3:1 hexanes:EtOAc), white solid, m.p. 237–238 ºС. IR
KBr) νmax 11 043, 1098, 1154, 1286, 1307, 1391, 1490, 1599,
705, 3035. H NMR (400 MHz, CDCl ) δ 1.29 (t, J = 7 Hz, 3 H,
(Ccycloprop.), 42.4 (CHcycloprop.), 52.0 (CO Me), 70.0 (CH), 118.3
(2C), 118.5, 127.7, 121.9, 123.1, 123.5, 124.8, 126.8, 127.1,
127.6 (4C), 128.0, 129.7 (4C), 130.7, 131.1, 131.2 (2C), 131.9,
2
3
CO CH CH ), 2.83 (s, 1 H, CHcycloprop.), 4.20-4.36 (m, 2 H,
CO CH CH ), 4.76 (s, 1 H, CH), 6.70–7.87 (m, 16 H, H ),
7
133.1, 135.0, 137.0, 141.9, 153.6, 157.1, 165.4 (CO), 170.1
2
2
3
+
(CO). HRMS (ESI): calcd. for С37
Н28NO
[M+H] 550.2013;
2
2
3
arom.
4
1
3
.81 (d, J = 8 Hz, 1 H, Harom.), 8.21 (d, J = 8 Hz, 1 H, Harom.).
C
found 550.2007.
NMR (100 MHz, CDCl ) δ 14.1 (CO CH CH ), 40.0 (Ccycloprop.),
3
2
2
3
4
1
1
1
1.9 (Ccycloprop.), 42.7 (CHcycloprop.), 61.1 (CO CH CH ), 70.0 (CH),
20.5, 123.5, 124.8, 125.1, 126.6, 127.0, 127.4 (4C), 127.5,
28.0, 131.1, 131.2, 131.4 (4C), 132.0, 133.2, 133.4, 135.2,
4.2.9. (1SR,1aRS,11bRS,11cSR)-Methyl 3-iodo-7-oxo-1a,11c-
diphenyl-1a,7,11b,11c-tetrahydro-1H-
2
2
3
cyclopropa[c]isoindolo[2,1-a]quinoline-1-carboxylate (7i) and
(1SR,1aRS,11bSR,11cSR)-methyl 3-iodo-7-oxo-1a,11c-diphenyl-
1a,7,11b,11c-tetrahydro-1H-cyclopropa[c]isoindolo[2,1-
a]quinoline-1-carboxylate (8i). Obtained as a 5:1 diastereomeric
mixture using general procedure from hydroxylactam 6e (281
mg, 0.8 mmol), cyclopropene 1b (200 mg, 0.8 mmol) and
37.4, 142.1, 165.5 (CO), 169.9 (CO). HRMS (ESI): calcd. for
+
С Н NNaO [M+Na] 494.1727; found 494.1727.
32
25
3
4
1
.2.7.
(1SR,1aRS,11bRS,11cSR)-Methyl
3-methoxy-7-oxo-
a,11c-diphenyl-1a,7,11b,11c-tetrahydro-1H-
cyclopropa[c]isoindolo[2,1-a]quinoline-1-carboxylate (7g) and
1SR,1aRS,11bSR,11cSR)-methyl 3-methoxy-7-oxo-1a,11c-
diphenyl-1a,7,11b,11c-tetrahydro-1H-cyclopropa[c]isoindolo-
2,1-a]quinoline-1-carboxylate (8g). Obtained as a 1.2:1 dia-
stereomeric mixture using general procedure from hydroxylactam
c (204 mg, 0.8 mmol), cyclopropene 1b (200 mg, 0.8 mmol)
and BF ⋅OEt (0.11 mL, 0.9 mmol) in 54% overall yield. Сrystal-
BF
zation of the 5:1 mixture from ethanol/CH
diastereomer 7i. Data for major diastereomer 7i: R
anes:EtOAc), light-gray solid, m.p. > 260 ºС. IR (KBr) ν 925,
1038, 1166, 1209, 1305, 1391, 1438, 1484, 1692, 3057. H NMR
3
⋅OEt
2
(0.11 mL, 0.9 mmol) in 64% overall yield. Recrystalli-
Cl gave pure major
0.35 (3:1 hex-
(
2
2
f
[
max
1
6
(400 MHz, CDCl ) δ 2.83 (s, 1 H, CHcycloprop.), 3.86 (s, 3 H,
3
CO Me), 4.74 (s, 1 H, CH), 6.62–6.97 (m, 4 H, Harom.), 7.04–7.22
3
2
2
lization of the 1.2:1 diastereomeric mixture from ethanol/CHCl3
solution by slow evaporation gave single crystals of diastereomer
(m, 7 H, Harom.), 7.26–7.34 (m, 2 H, Harom.), 7.63 (d, J = 9 Hz, 1
H, Harom.), 7.68 (s, 1 H, Harom.), 7.82 (d, J = 8 Hz, 1 H, Harom.),
13
7
g suitable for X-ray analysis. Data for diastereomer 7g: R 0.33
8.01 (d, J = 9 Hz, 1 H, Harom.). C NMR (100 MHz, CDCl
Me),
69.8 (CH), 88.8 (I-Carom.), 122.4, 123.5, 124.7, 127.0, 127.1,
3
) δ
f
(2:1 hexanes:EtOAc), white solid, m.p. 212–215 ºС. IR (KBr)
39.1 (Ccycloprop.), 41.6 (Ccycloprop.), 42.4 (CHcycloprop.), 52.1 (CO
2
νmax 933, 1045, 1100, 1170, 1234, 1271, 1399, 1447, 1504, 1606,

9
1
1
27.7 (4C), 128.1, 131.0 (4C), 131.3, 131.5, 131.6, 132.7, 135.0,
(400 MHz, CDCl ) δ 3.71 (s, 3 Н, CO Me), 4.07 (d, J = 16 Hz,
ACCEPTED MANUSCRIPT
3
2
35.5, 136.5, 139.8, 141.8, 165.4 (CO), 169.8 (CO). HRMS
1 Н from СН ), 4.84 (s, 1 Н, CH), 5.58 (d, J = 16 Hz, 1 Н from
СН ), 5.72 (s, 1 Н, СН), 6.66 (d, J = 8 Hz, 1 H, Harom.), 7.05–7.43
2
+
(ESI): calcd. for С Н INO [M+H] 584.0718; found 584.0723.
31
23
3
2
(
m, 13 Н, H ), 7.43–7.58 (m, 3 Н, Harom.), 8.02 (d, J = 8 Hz, 1
arom.
13
4
.2.10. (1aRS,11bSR,11cSR)-Methyl 3-methyl-7-oxo-1,1,1a-
H, Harom.). C NMR (100 MHz, CDCl ) δ 44.3 (CH ), 52.5
3 2
triphenyl-1a,7,11b,11c-tetrahydro-1H-cyclopropa[c]isoindolo-
2,1-a]quinoline-11c-carboxylate (15a). Obtained as single dia-
(CO Me), 57.3 (CH), 59.0 (CH), 120.7, 122.8, 123.3, 124.0,
2
[
126.2, 127.5, 128.1 (3C), 128.4, 128.6 (2C), 128.7 (5C), 132.0
(2C), 134.4, 136.1, 137.2, 140.7, 141.8, 143.6, 147.3, 168.9
stereomer using general procedure from hydroxylactam 6b (191
mg, 0.8 mmol), cyclopropene 1h (261 mg, 0.8 mmol) and
BF ⋅OEt (0.11 mL, 0.9 mmol) in 18% yield (79 mg). R 0.40 (3:1
+
(CO), 170.3 (CO). HRMS (ESI): calcd. for С Н NO [M+H]
32
26
3
472.1908; found 472.1886.
3
2
f
hexanes:EtOAc), white solid, m.p. 258–259 ºС. IR (KBr) ν
max
1
9
11, 1095, 1227, 1390, 1498, 1698, 1736, 2947, 3022, 3050. H
4.3.2. Methyl 3-(2-(2,4-dichlorobenzyl)-1-oxoisoindolin-3-yl)-2-
phenyl-1H-indene-1-carboxylate (12b). Obtained as a 2:1 dia-
stereomeric mixture using general procedure from hydroxylactam
11b (62 mg, 0.2 mmol), cyclopropene 1b (50 mg, 0.2 mmol) and
NMR (400 MHz, CDCl ) δ 2.31 (s, 3 H, Me), 2.91 (s, 3 H,
3
CO Me), 5.10 (s, 1 H, CH), 6.89–7.19 (m, 13 H, Harom.), 7.27–
2
7
.38 (m, 2 H, Harom.), 7.55–7.63 (m, 4 H, Harom.), 7.72 (d, J = 8
13
Hz, 1 H, Harom.), 7.96 (d, J = 8 Hz, 2 H, Harom.). C NMR (100
BF
lization of the 2:1 mixture from methanol gave pure major dia-
stereomer. Data for major diastereomer 12b: R 0.34 (3:1 hex-
3 2
⋅OEt (0.03 mL, 0.22 mmol) in 53% overall yield. Recrystal-
MHz, CDCl ) δ 21.4 (Me), 42.0 (Ccycloprop.), 45.2 (Ccycloprop.), 50.3
3
(
Ccycloprop.), 50.8 (CO Me), 61.2 (CH), 120.3, 123.7, 124.1, 126.2
f
2
(2C), 126.6 (2C), 126.9, 127.2 (2C), 128.3, 128.9, 129.0 (2C),
anes:EtOAc), white solid, m.p. 162–165 ºС. IR (KBr) νmax 908,
1
1
29.6, 131.2, 131.5 (2C), 131.8 (2C), 132.5 (2C), 133.2, 133.3,
1016, 1049, 1142, 1218, 1298, 1402, 1468, 1563, 1590, 1694,
1
33.5, 133.6, 139.5, 140.0, 140.3, 141.5, 164.9 (CO), 167.7
1736, 2950, 3057. H NMR (400 MHz, CDCl ) δ 3.59 (s, 3 Н,
3
+
(CO). HRMS (ESI): calcd. for C H NO [M+H] 548.2221;
CO Me), 4.25 (d, J = 16 Hz, 1 Н from СН ), 4.97 (s, 1 Н, CH),
38
30
3
2
2
found 548.2226.
5.02 (d, J = 16 Hz, 1 Н from СН ), 5.78 (s, 1 Н, СН), 6.47 (d, J =
2
8
Hz, 1 H, Harom.), 6.84 (d, J = 8 Hz, 1 H, Harom.), 6.95 (d, J = 8
4
.2.11. (1aRS,11bSR,11cSR)-Methyl 3-methoxy-7-oxo-1,1,1a-
Hz, 1 H, Harom.), 7.03-7.10 (m, 2 Н, Harom.), 7.18 (t, J = 8 Hz, 1 H,
Harom.), 7.31–7.40 (m, 5 Н, Harom.), 7.53 (d, J = 8 Hz, 1 H, Harom.),
triphenyl-1a,7,11b,11c-tetrahydro-1H-cyclopropa[c]isoindo-
lo[2,1-a]quinoline-11c-carboxylate (15b). Obtained as single
diastereomer using general procedure from hydroxylactam 6c
1
3
7.59–7.67 (m, 3 Н, Harom.), 8.02–8.09 (m, 1 Н, Harom.). C NMR
(100 MHz, CDCl ) δ 41.5 (CH ), 52.5 (CO Me), 57.1 (CH), 57.9
3
2
2
(
204 mg, 0.8 mmol), cyclopropene 1h (261 mg, 0.8 mmol) and
(CH), 120.8, 123.0, 123.4, 124.3, 126.2, 126.9, 128.2, 128,4
(2C), 128.7 (2C), 129.0, 129.1, 129.4, 130.9, 132.2, 132.4, 132.6,
133.6, 133.8, 133.9, 134.8, 140.3, 141.6, 144.0, 147.8, 168.7
BF ⋅OEt (0.11 mL, 0.9 mmol) in 24% yield (108 mg). R 0.24
3
2
f
(3:1 hexanes:EtOAc), white solid, m.p. 253–254 ºС. IR (KBr)
3
5
νmax 1041, 1164, 1217, 1270, 1398, 1504, 1615, 1694, 1720,
2
(CO), 170.1 (CO). HRMS (ESI): calcd. for С32
Н24 Cl
2
NO
3
1
+
833, 2929, 3062. H NMR (400 MHz, CDCl ) δ 2.96 (s, 3 H,
[M+H] 540.1128; found 540.1133.
3
CO Me), 3.75 (s, 3 H, MeO), 5.10 (s, 1 H, CH), 6.79 (d, J = 8
Hz, 3 H, Harom.), 7.05–7.13 (m, 9 H, Harom.), 7.20 (t, J = 8 Hz, 1 H,
Harom.), 7.33 (t, J = 8 Hz, 2 H, Harom.), 7.59–7.61 (m, 4 H, Harom.),
2
4.3.3.
(SR)-3-((RS)-1,2-Diphenyl-1H-inden-3-yl)-2-p-tolyliso-
indolin-1-one (13a) and (RS)-3-((RS)-1,2-diphenyl-1H-inden-3-
yl)-2-p-tolylisoindolin-1-one (14a). Obtained as a 3.4:1 diastere-
omeric mixture using general procedure from hydroxylactam 6b
(48 mg, 0.2 mmol), cyclopropene 1c (54 mg, 0.2 mmol) and
7
.71 (d, J = 8 Hz, 1 H, Harom.), 7.96 (d, J = 8 Hz, 1 H, Harom.), 8.00
13
(
(
(
d, J = 8 Hz, 1 H, Harom.). C NMR (100 MHz, CDCl ) δ 42.5
Ccycloprop.), 45.2 (Ccycloprop.), 50.1 (Ccycloprop.), 50.9 (CO Me), 55.5
MeO), 61.3 (CH), 113.1, 118.5, 121.7, 123.8, 124.1, 126.2,
3
2
BF
lization of the 3.4:1 mixture from methanol/CH
major diastereomer 13a. Data for major diastereomer 13a: R
(3:1 hexanes:EtOAc), white solid, m.p. 205–208 ºС. IR (KBr)
⋅OEt
(0.03 mL, 0.22 mmol) in 59% overall yield. Recrystal-
Cl gave pure
0.43
3
2
1
1
1
26.4, 126.4 (2C), 127.1, 127.3 (2C), 128.9, 129.1 (2C), 129.1,
31.1, 131.3, 131.5 (2C), 131.9 (2C), 132.6 (2C), 133.7, 139.3,
2
2
f
39.7, 140.3, 141.3, 155.8, 164.8 (CO), 167.5 (CO). HRMS
+
(ESI): calcd. for C H KNO [M+K] 602.1729; found 602.1730.
ν
max 906, 1029, 1110, 1138, 1218, 1295, 1370, 1466, 1513, 1596,
38
29
4
1
1
693, 1894, 2918, 3045, 3367. H NMR (400 MHz, CDCl ) δ
3
4
.3. General procedure for the synthesis of 3-(1H-inden-3-
2.40 (s, 3 Н, Me), 4.75 (s, 1 Н, CH), 6.20 (s, 1 Н, СН), 6.46–6.75
(m, 3 Н, Harom.), 6.92–7.48 (m, 15 Н, Harom.), 7.51–7.72 (m, 3 Н,
yl)isoindolin-1-one derivatives.
13
Harom.), 8.09–8.18 (m, 1 Н, Harom.). C NMR (100 MHz, CDCl ) δ
3
BF ⋅OEt (0.22 mmol) was added to vigorously stirred solu-
tion of the cyclopropene 1b, 1c (0.2 mmol) and hydroxylactam
b–e, 6h, 11a–b (0.2 mmol) in anhydrous dichloromethane (5
21.1 (Me), 60.0 (CH), 60.3 (CH), 123.0, 123.9, 124.4, 125.2
(2C), 125.9, 126.9, 127.0, 128.1, 128.4 (4C), 128.6 (2C), 128.9
(3C), 129.0, 129.4 (2C), 132.4, 132.7, 134.1, 134.3, 135.6, 135.9,
3
2
6
mL) under an argon atmosphere. The reaction mixture was stirred
at room temperature for 16 h (monitored by TLC), the solvent
was evaporated under reduced pressure. The residue was purified
by silica gel chromatography (2:1 hexane:ethyl acetate) to give
products 12a–b, 13a–e, 14a–e as summarized in Table 4.
138.0, 141.0, 143.6, 148.4, 153.4, 167.8 (CO). HRMS (ESI):
+
calcd. for С36
Н28NO [M+H] 490.2166; found 490.2154.
4.3.4. (SR)-2-(4-Chlorophenyl)-3-((RS)-1,2-diphenyl-1H-inden-
3-yl)isoindolin-1-one (13b) and (RS)-2-(4-chlorophenyl)-3-((RS)-
1
,2-diphenyl-1H-inden-3-yl)isoindolin-1-one (14b). Obtained as a
4
.3.1. Methyl 3-(2-benzyl-1-oxoisoindolin-3-yl)-2-phenyl-1H-
3.7:1 diastereomeric mixture using general procedure from hy-
indene-1-carboxylate (12a). Obtained as a 3:1 diastereomeric
mixture using general procedure from hydroxylactam 11a (48
mg, 0.2 mmol), cyclopropene 1b (50 mg, 0.2 mmol) and
BF ⋅OEt (0.03 mL, 0.22 mmol) in 56% overall yield. Recrystal-
droxylactam 6h (52 mg, 0.2 mmol), cyclopropene 1c (54 mg, 0.2
mmol) and BF ⋅OEt (0.03 mL, 0.22 mmol) in 66% overall yield.
3 2
Data for the 3.7:1 diastereomeric mixture: white solid. IR (KBr)
νmax 903, 1014, 1090, 1141, 1209, 1365, 1413, 1493, 1597, 1699,
3
2
1
lization of the 3:1 mixture from methanol gave pure major dia-
3025. H NMR (400 MHz, CDCl , major diastereomer 13b) δ
3
stereomer. Data for major diastereomer 12a: R 0.29 (3:1 hex-
4.71 (s, 1 Н, CH), 6.20 (s, 1 Н, СН), 6.44–8.11 (m, 22 Н, Harom.).
f
13
anes:EtOAc), white solid, m.p. 172–174 ºС. IR (KBr) ν 1028,
C NMR (100 MHz, CDCl
3
, major diastereomer 13b) δ 59.8
max
1
1
145, 1199, 1261, 1401, 1467, 1692, 1737, 2914, 3062. H NMR
(CH), 60.0 (CH), 120.2, 123.1, 124.1, 124.5, 125.9 (2C), 126.0,

1
0
Tetrahedron
ACCEPTED MANUSCRIPT
1
27.0, 127.2, 128.1, 128.2 (2C), 128.3 (2C), 128.5 (2C), 128.6
Acknowledgements
(2C), 128.7 (4C), 128.8, 128.9, 129.1, 132.8, 135.4, 137.6, 140.7,
1
43.4, 148.4, 153.8, 167.4 (CO). HRMS (ESI): calcd. for
We gratefully acknowledge the financial support from the
Russian Science Foundation (Project No 14-13-00126). This
research made use of resources from the X-ray Diffraction
Centre, Centre for Magnetic Resonance, Educational Resourse
Center of Chemistry, Centre for Chemical Analysis and Materials
and the Center for optical and laser materials research of Saint-
Petersburg State University.
35
+
С Н ClNO [M+H] 510.1620; found 510.1614.
35
25
4
.3.5. (SR)-2-(4-Iodophenyl)-3-((RS)-1,2-diphenyl-1H-inden-3-
yl)isoindolin-1-one (13c) and (RS)-2-(4-iodophenyl)-3-((RS)-1,2-
diphenyl-1H-inden-3-yl)isoindolin-1-one (14c). Obtained as a 4:1
diastereomeric mixture using general procedure from hydrox-
ylactam 6e (70 mg, 0.2 mmol), cyclopropene 1c (54 mg, 0.2
mmol) and BF ⋅OEt (0.03 mL, 0.22 mmol) in 74% overall yield.
Supplementary Material
3
2
Data for the 4:1 diastereomeric mixture: light-gray solid. IR
Supplementary data (experimental procedures, characteriza-
tion data, and copies of NMR, UV/vis absorption and fluores-
cence spectra) associated with this article can be found in the
online version, at doi:
1
(
KBr) νmax 1005, 1140, 1364, 1404, 1488, 1602, 1699, 3023. H
NMR (400 MHz, CDCl , major diastereomer 13c) δ 4.71 (s, 1 Н,
3
CH), 6.21 (s, 1 Н, СН), 6.44 (d, J = 8 Hz, 2 Н, Harom.), 6.57 (d, J
=
8 Hz, 1 H, Harom.), 6.96–7.07 (m, 7 Н, Harom.), 7.17–7.26 (m, 4
Н, Harom.), 7.34–7.39 (m, 3 Н, Harom.), 7.58–7.63 (m, 4 Н, Harom.),
References and notes
13
8
.10–8.15 (m, 1 Н, Harom.). C NMR (100 MHz, CDCl , major
3
diastereomer 13c) δ 59.6 (CH), 60.1 (CH), 89.9 (I-Carom.), 120.2,
1.
(a) Rubin, M.; Rubina, M.; Gevorgyan, V. Chem. Rev. 2007, 107,
3117; (b) Rubin, M.; Rubina, M.; Gevorgyan, V. Synthesis 2006,
1221; (c) Methods of Organic Chemistry (Houben-Weyl); A. de
Meijere, Ed.; Thieme: Stuttgart, Germany, 1997; Vol. E17a-d; (d)
Baird, M. S. Chem. Rev. 2003, 103, 1271; (e) Dolbier, Jr., W. R.;
Battiste, M. A. Chem. Rev. 2003, 103, 1071.
1
1
1
1
6
23.0, 124.1, 124.3, 124.5, 126.0, 126.2 (2C), 127.0, 127.2,
28.4, 128.5 (2C), 128.6 (2C), 128.7 (2C), 128.8 (2C), 132.4,
32.8, 133.7, 135.5, 136.7, 137.6, 137.8 (2C), 140.7, 143.4,
+
48.4, 153.7, 167.3. HRMS (ESI): calcd. for С Н INO [M+H]
35
25
02.0976; found 602.0970.
2
.
(a) Zhu, Z.-B.; Wei, Y.; Shi, M. Chem. Soc. Rev. 2011, 40, 5534;
(b) Yang, J.; Šečkutė, J.; Cole, C. M.; Devaraj, N. K. Angew.
4
3
.3.6. (SR)-2-(4-Methoxyphenyl)-3-((RS)-1,2-diphenyl-1H-inden-
-yl)isoindolin-1-one (13d) and (RS)-2-(4-methoxyphenyl)-3-
Chem. Int. Ed. 2012, 51, 7476; (c) Yu, Z.; Pan, Y.; Wang, Z.;
Wang, J.; Lin, Q. Angew. Chem. Int. Ed. 2012, 51, 10600; (d)
Song, C.; Ju, L.; Wang, M.; Liu, P.; Zhang, Y.; Wang, J.; Xu, Z.
Chem. Eur. J. 2013, 19, 3584; (e) Komatsu, K.; Kitagawa, T.
Chem. Rev. 2003, 103, 1371; (f) Hadfield, M. S.; Bauer, J. T;
Glen, P. E.; Lee, A.-L. Org. Biomol. Chem. 2010, 8, 4090; (g)
Gallego, G.; Ariafard, A.; Tran, K.; Sandoval, D.; Choi, L.; Chen,
Y.-H.; Yates, B. F.; Tao, F.-M.; Hyland, C. J. T. Org. Biomol.
Chem. 2011, 9, 3359; (h) Miege, F., Meyer, C.; Cossy, J. Org.
Lett. 2010, 12, 248; (i) Krämer, K.; Leong, P.; Lautens, M. Org.
Lett. 2011, 13, 819; (j) Liu, Y.; Ma, S. Org. Lett. 2012, 14, 720;
(k) Young, P. C.; Hadfield, M. S.; Arrowsmith, L.; Macleod, K.
M.; Mudd, R. J.; Jordan-Hore, J. A.; Lee, A.-L. Org. Lett. 2012,
((RS)-1,2-diphenyl-1H-inden-3-yl)isoindolin-1-one (14d). Ob-
tained as a 4.6:1 diastereomeric mixture using general procedure
from hydroxylactam 6c (51 mg, 0.2 mmol), cyclopropene 1c (54
mg, 0.2 mmol) and BF ⋅OEt (0.03 mL, 0.22 mmol) in 60% over-
all yield. Recrystallization of the 4.6:1 mixture from metha-
nol/CH Cl gave pure major diastereomer 13d. Data for major
diastereomer 13d: R 0.28 (3:1 hexanes:EtOAc), white solid, m.p.
1
1
Н, MeO), 4.77 (s, 1 Н, CH), 6.15 (s, 1 Н, СН), 6.47–6.75 (m, 3
Н, Harom.), 6.81–7.45 (m, 16 Н, Harom.), 7.51–7.70 (m, 2 Н, Harom.),
8
3
2
2
2
f
98–200 ºС. IR (KBr) ν 1031, 1143, 1248, 1301, 1384, 1466,
max
1
513, 1595, 1690, 3022. H NMR (400 MHz, CDCl ) δ 3.84 (s, 3
3
1
4, 898.
3
4
.
.
(a) Nakamura, E.; Isaka, M.; Matsuzawa, S. J. Am. Chem. Soc.
1988, 113, 1297; (b) Kubato, K.; Mori, S.; Nakamura, M.;
Nakamura, E. J. Am. Chem. Soc. 1998, 120, 13334.
(a) Padwa, A.; Blacklock, T. J.; Loza, R. J. Org. Chem. 1982, 47,
3712; (b) Al-Dulayymi, J.; Baird, M. S.; Clegg, W. Tetrahedron
Lett. 1988, 47, 6149; (c) Müller, P.; Pautex, N. Helv. Chim. Acta,
13
.07–8.13 (m, 1 Н, Harom.). C NMR (100 MHz, CDCl ) δ 55.5
3
(MeO), 59.9 (CH), 60.6 (CH), 114.2 (2C), 120.5, 123.0, 124.0,
1
1
1
24.3, 125.9, 127.0 (2C), 127.1 (2C), 128.0, 128.1, 128.4 (4C),
28.5 (2C), 128.9 (3C),129.8, 132.3, 134.1, 135.5, 138.0, 141.1,
1
991, 74, 55.
5. (a) Franck-Neumann, M.; Buchecker, C.; Angew. Chem. Int. Ed.
973, 12, 240; (b) Binger, P.; Wedemann, P.; Goddard, R.; Brink-
43.7, 148.4, 153.7, 158.1, 167.7 (CO). HRMS (ESI): calcd. for
+
С Н NO [M+H] 506.2115; found 506.2123.
36
28
2
1
er, U. H. J. Org. Chem. 1996, 61, 6462; (c) Diev, V. V.; Kostikov,
R. R.; Gleiter, R.; Molchanov, A. P. J. Org. Chem. 2006, 71,
4066; (d) Diev, V. V.; Stetsenko, O. N.; Tung, T. Q.; Kopf, J.;
Kostikov, R. R.; Molchanov, A. P. J. Org. Chem. 2008, 73, 2396.
(a) Ma, S.; Zhang, J.; Lu, L.; Jin, X.; Cai, Y.; Hou, H. Chem.
Commun. 2005, 909; (b) Xu, X.; Zavalij, P. J.; Doyle, M. P.
Chem. Commun. 2013, 49, 10287; (c) Chen, S.; Ren, J.; Wang, Z.
Tetrahedron 2009, 65, 9146.
4
3
.3.7. (SR)-2-(4-Phenoxyphenyl)-3-((RS)-1,2-diphenyl-1H-inden-
-yl)isoindolin-1-one (13e) and (RS)-2-(4-phenoxyphenyl)-3-
((RS)-1,2-diphenyl-1H-inden-3-yl)isoindolin-1-one (14e). Ob-
6
.
tained as 3:1 diastereomeric mixture using general procedure
from hydroxylactam 6d (64 mg, 0.2 mmol), cyclopropene 1c (54
mg, 0.2 mmol) and BF ⋅OEt (0.03 mL, 0.22 mmol) in 65% over-
3
2
all yield. Recrystallization of the 3:1 mixture from metha-
7. (a) Othman, R. B.; Affani, R.; Tranchant, M.-J.; Antoniotti, S.;
Dalla, V. Angew. Chem. Int. Ed. 2010, 49, 776; (b) Maryanoff, B.
E.; Zhang, H.-C.; Cohen, J. H.; Turchi, I. J.; Maryanoff, C. A.
Chem. Rev. 2004, 104, 1431; (c) Speckamp, W. N.; Moolenaar,
M. J. Tetrahedron 2000, 56, 3817.
8. (a) Bahajaj, A. A.; Vernon, J. M.; Wilson, G. D. J. Chem. Soc.,
Perkin Trans. 1 2001, 1446; (b) Katritzky, A. R.; Mehta, S.; He,
H.-Y. J. Org. Chem. 2001, 66, 148; (c) Raheem, I. T.; Thiara, P.
S.; Peterson, E. A.; Jacobsen, E. N. J. Am. Chem. Soc. 2007, 129,
nol/CH Cl gave pure major diastereomer 13e. Data for major
2
2
diastereomer 13e: R 0.38 (3:1 hexanes:EtOAc), white solid, m.p.
f
1
1
6
88–190 ºС. IR (KBr) ν 1099, 1154, 1231, 1381, 1505, 1586,
max
1
705, 3058. H NMR (400 MHz, CDCl ) δ 4.77 (s, 1 Н, CH),
3
.16 (s, 1 Н, СН), 6.58 (d, J = 8 Hz, 2 H, Harom.), 6.63 (d, J = 7
Hz, 1 H, Harom.), 6.94–7.37 (m, 20 Н, Harom.), 7.53–7.62 (m, 3 Н,
13
Harom.), 8.10–8.14 (m, 1 Н, Harom.). C NMR (100 MHz, CDCl3)
δ 60.0 (CH), 60.5 (CH), 119.0 (2C), 119.04 (2C), 120.5, 123.0,
1
3404; (d) King, F. D.; Aliev, A. E.; Caddick, S.; Tocher, D. A.
Org. Biomol. Chem. 2011, 9, 1547; (e) Hilt, G.; Galbiati, F.;
Harms, K. Synthesis 2006, 21, 3575; (f) Allin, S. M.; James, S. L.;
Martin, W. P.; Smith, T. A. D. Tetrahedron Lett. 2001, 42, 3943;
1
23.5, 124.1, 124.4, 125.9, 127.0 (3C), 128.1, 128.4 (3C), 128.5
(2C), 128.6 (2C), 128.8 (2C), 129.0, 129.8 (2C), 132.1, 132.5
(g) Allous, I.; Comesse, S.; Berkeš, D.; Alkyat, A.; Daїch, A. Tet-
(
1
5
2C), 133.9, 135.4, 137.9, 141.0, 143.6, 148.3, 153.8, 155.6,
+
rahedron Lett. 2009, 50, 4411; (h) Stepakov, A. V.; Ledovskaya,
M. S.; Boitsov, V. M.; Molchanov, A. P.; Kostikov, R. R.;
Gurzhiy, V. V.; Starova, G. L. Tetrahedron Lett. 2012, 53, 5414;
57.0, 167.7 (CO). HRMS (ESI): calcd. for С Н NO [M+H]
41 30 2
68.2272; found 568.2274.

1
1
(
i) Ledovskaya, M. S.; Molchanov, A. P.; Boitsov, V. M.; Kos-
ACCEPTED MANUSCRIPT
tikov, R. R.; Stepakov, A. V. Tetrahedron, 2015, 71, 1952; (j) Le-
dovskaya, M. S.; Stepakov, A. V.; Molchanov, A. P.; Kostikov, R.
R. Tetrahedron, 2015, 71, 7562.
9
.
(a) Qiao, L.; Zhou, Y.; Zhang, W. Chin. J. Chem. 2010, 28, 449;
(
b) Zhang, W.; Zhen, A.; Liu, Z.; Yang, L.; Liu, Z. L. Tetrahedron
Lett. 2005, 46, 5691; (c) Zhang, W.; Huang, L.; Wang, J. Synthesis
006, 2053; (d) Jha, A.; Chou, T.-Y.; ALJaroudi, Z.; Ellis, B. D.;
Cameron, T. S. Beilstein J. Org. Chem. 2014, 10, 848.
2
1
1
0. Stepakov, A. V.; Larina, A. G.; Boitsov, V. M.; Gurzhiy, V. V.;
Molchanov, A. P.; Kostikov, R. R. Tetrahedron Lett. 2014, 55,
2
022.
1. (a) Azumaya, I.; Kagechika, H.; Fujiwara, Y.; Itoh, M.;
Yamaguchi, K.; Shudo, K. J. Am. Chem. Soc. 1991, 113, 2833; (b)
Lewis, F. D.; Liu, W. J. Phys. Chem. A 2002, 106, 1976; (c)
Lhiaubet-Vallet, V.; Trzcionka, J.; Encinas, S.; Miranda, M. A.;
Chouini-Lalanne, N. J. Phys. Chem. B 2004, 108, 14148; (d) Tsu-
ruta, Y.; Date, Y.; Kohashi, K. J. Chromat. 1990, 502, 178; (e)
Trzcionka, J.; Noirot, A.; Fabre, P.-L.; Chouini-Lalanne, N. Pho-
tochem. Photobiol. Sci. 2005, 4, 298.
1
1
2. Mase, N.; Nishi, T.; Ichihara, K.; Bessho, J.; Yoda, H.; Tabake, K.
J. Chem. Soc., Perkin Trans. I 2002, 707.
3. (a) D'yakonov, I. A.; Komendantov, M. I.; Gokhmanova, I.; Kos-
tikov, R. R. Zhurnal Obshchei Khimii (USSR) 1959, 29, 3848; (b)
D'yakonov, I. A.; Komendantov, M. I. Zhurnal Obshchei Khimii
(
USSR) 1961, 31, 3881; (с) Fedorov, A. A. ; Duisenbaev, Sh. E.;
Razin, V. V.; Kuznetsov, M. A.; Linden, E. Russ. J. Org. Chem.
007, 43, 231; (d) Plotkin, V. N.; Domnin, I. N.; Dmitrieva, E. F.;
Komendantov, M. I. J. Org. Chem. (USSR) 1987, 23, 1115.
2